Oxyranyle-triazoline thiones and their use as microbicides

ABSTRACT

Novel oxiranyl-triazolinethiones of the formula                    
     in which 
     R 1 , R 2  and R 3  are each as defined in the description, 
     a process for preparing the novel substances and their use as microbicides in crop protection and in the protection of materials.

The present invention relates to novel oxiranyl-triazolinethiones, to aprocess for their preparation and to their uses as microbicides.

It is already known that numerous azolylmethyl-oxirane derivatives havefungicidal properties (cf. EP-A 0 094 564, EP-A 0 196 038 and WO-A 96-38440). Thus, for example,3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)2-[(4,5-dihydro-5-thiono-1,2,4-triazol-1-yl)-methyl]-oxiranecan be used for controlling fungi. The activity of this substance isgood; however, it is sometimes unsatisfactory at low application rates.

This invention, accordingly, provides novel oxiranyl-triazolinethionesof the formula

in which

R¹ represents alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1to 4 carbon atoms and 1 to 5Halogen atoms, optionallyhalogen-substituted cycloalkyl having 3 to 7 carbon atoms, naphthyl orphenyl which is optionally mono- to trisubstituted by identical ordifferent substituents from the group consisting of halogen, nitro,phenyl, phenoxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5Halogenatoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5Halogen atomsand halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5Halogenatoms,

R² represents phenyl which is optionally mono- to trisubstituted byidentical or different substituents from the group consisting ofhalogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbonatoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5Halogen atoms,halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5Halogen atoms andhalogenoalkylthio having 1 to 4 carbon atoms and 1 to 5Halogen atoms and

R³ represents alkoxyalkyl, isopropyl or n-dodecyl.

The substances according to the invention contain two asymmetricallysubstituted carbon atoms and can therefore be obtained in the form ofdiastereomers or enantiomers. The present invention relates both to theindividual isomers and to their mixtures.

Furthermore, it has been found that oxiranyl-triazolinethiones of theformula (I) or (Ia) are obtained when oxirane derivatives of the formula

in which

R¹ and R² are each as defined above are reacted with isocyanates of theformula

R³—NCO  (III),

in which

R³ is as defined above,

if appropriate in the presence of a catalyst and if appropriate in thepresence of a diluent.

Finally, it has been found that the novel oxiranyl-triazolinethiones ofthe formula (I) or (Ia) have very good microbicidal properties and canbe used both in crop protection and in the protection of materials forcontrolling undesirable microorganisms.

Surprisingly, the oxiranyl-triazolinethiones of the formula (I) or (Ia)according to the invention have better microbicidal activity, inparticular fungicidal activity, than the constitutionally most similarprior-art compounds of the same direction of action. Thus, thesubstances according to the invention surpass3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)-2-[(4,5-dihydro-5-thiono-1,2,4-triazol-1-yl)-methyl]-oxiranewith respect to the fungicidal properties.

The formula (I) or (Ia) provides a general definition of theoxiranyl-triazolinethiones according to the invention.

R¹ preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, iso-butyl, tert-butyl, fluoro-tert-butyl,difluoro-tert-butyl, cycloalkyl having 3 to 6 carbon atoms which isoptionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine andbromine, preferably represents naphthyl or preferably represents phenylwhich may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,nitro, phenyl, phenoxy, methyl, ethyl, tert-butyl, methoxy, ethoxy,trifluoromethyl, trichloromethyl, difluoromethyl, difluorochloromethyl,trifluoromethoxy, difluoromethoxy and trifluoromethylthio,

R² preferably represents phenyl which may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl,methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl,difluorochloromethyl, trifluorometboxy, difluoromethoxy andtrifluoromethylthio, and

R³ preferably represents alkoxyalkyl having 1 to 6 carbon atoms in thealkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety and alsopreferably represents isopropyl or n-dodecyl.

Particular preference is given to oxiranyl-triazolinethiones of theformula (I) or (Ia) in which

R¹ represents phenyl which may be mono- to trisubstituted by identicalor different substituents from the group consisting of fluorine,chlorine, bromine, nitro, phenyl, phenoxy, methyl, ethyl, tert-butyl,methoxy, ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl,difluorochloromethyl, trifluoromethoxy, difluoromethoxy andtrifluoromethylthio,

R² represents phenyl which may be mono- to trisubstituted by identicalor different substituents from the group consisting of fluorine,chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy,ethoxy, trifluoromethyl, trichloromethyl, difluoromethyl,difluorochloromethyl, trifluorometboxy, difluoromethoxy andtrifluoromethylthio,

and

R³ represents alkoxyalkyl having 1 to 4 carbon atoms in the alkoxymoiety and 1 to 4 carbon atoms in the alkyl moiety and also representsisopropyl or n-dodecyl.

The substituent definitions mentioned can be combined with one anotherat will. Moreover, individual definitions may not apply.

The oxirane derivatives required as starting materials for preparing thesubstances according to the invention can be present in the “thiono”form of the formula

or in the tautomeric “mercapto” form of the formula

It is therefore possible that the substances according to the inventioncan be derived both from the “thiono” form of the formula (II) and fromthe “mercapto” form of the formula (IIa). This means that the substancesaccording to the invention are either present as substances of theformula

or of the formula

or as mixtures of the formulae (I) and (Ia).

Examples of substances according to the invention which may be mentionedare the oxiranyl-triazolinethiones listed in the table below.

TABLE 1

R¹ R² R³

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH_(2—O—CH) ₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—CH₂—CH₂—O—CH₃

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—CH₃

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

—(CH₂)₃—O—C₂H₅

Using3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)2-[(4,5-dihydro-5-thiono-1,2,4-triazol-1-yl)-methyl]oxiraneas starting material and 3-ethoxy-propyl isocyanate as reactioncomponent, the course of the process according to the invention can beillustrated by the scheme below.

The formula (II) or (IIa) provides a general definition of the oxiranederivatives required as starting materials for carrying out the processaccording to the invention. In this formula, R¹ and R² preferably havethose meanings which have already been mentioned in connection with thedescription of the substances of the formula (I) or (Ia) according tothe invention as being preferred for these radicals.

The oxirane derivatives of the formula (II) or (IIa) are already known(cf. WO-A 96-38 440).

The formula (III) provides a general definition of the isocyanatesrequired as reaction components for carrying out the process accordingto the invention. In this formula, R³ preferably has those meaningswhich have already been mentioned in connection with the description ofthe substances of the formula (I) according to the invention as beingpreferred for this radical.

The isocyanates of the formula (III) are known or can be prepared byknown methods.

Suitable catalysts for carrying out the process according to theinvention are all reaction promoters which are customary for suchreactions. Preference is given to using amines, such as triethylamine,pyridine, dimethylaminopyridine and diazabicyclo-undecene (DBU).

Suitable diluents for carrying out the process according to theinvention are all inert organic solvents which are customary for suchreactions. Preference is given to using aromatic hydrocarbons, such astoluene, xylene or decaline, also halogenated hydrocarbons, such asdichloromethane, chloroform, carbon tetrachloride, dichloroethane ortrichloroethane, moreover ethers, such as diethyl ether, diisopropylether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane ortetrahydrofuran, and furthermore nitrites, such as acetonitrile,propionitrile, n- or iso-butyronitrile.

When carrying out the process according to the invention, the reactiontemperatures can be varied within a certain range. In general, theprocess is carried out at temperatures between −20° C. and +100° C.,preferably between 0° C. and +80° C.

The process according to the invention is generally carried out underatmospheric pressure. However, it is also possible to carry out theprocess under elevated pressure or, if no highly volatile components aretaking part in the reaction, also under reduced pressure.

When carrying out the process according to the invention, in generalfrom 1 to 1.5 mol of isocyanate of the formula (III) and a small amountof catalyst are employed per mole of oxirane derivative of the formula(II) or (IIa). Work-up is carried out by customary methods. In general,the reaction mixture is concentrated under reduced pressure and theproduct that remains is freed from any impurities that may still bepresent by customary methods, for example by recrystallization orchromatography.

The compounds according to the invention have a potent microbicidalactivity and can be employed for controlling undesirable microorganisms,such as fungi and bacteria, in crop protection and in the protection ofmaterials.

Fungicides are employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides are employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above may be mentioned as examples, but not byway of limitation:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae,

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae; and

Pseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

The active compounds according to the invention can be employed inparticular for controlling Pyricularia oryzae on rice and forcontrolling cereal diseases, such as Puccinia, Erysiphe and Fusariumspecies. Moreover, the substances according to the invention can be usedsuccessfully against Venturia, Podosphaera and Sphaerotheca. They alsohave very good in-vitro action.

The active compounds according to the invention may also be employed toincrease the yield of crops. Moreover, they have low toxicity and arewell tolerated by plants.

In the protection of materials, the compounds according to the inventioncan be employed for protecting industrial materials against infectionwith, and destruction by, undesired microorganisms.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or decomposed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the proliferation of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably adhesives, sizes, paper and board, leather,wood, paints, cooling lubricants and beat-transfer liquids, particularlypreferably wood.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discolouringand wood-destroying fungi (Basidiomycetes), and against slime organismsand algae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa, and

Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted into the customary formulations, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsulations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. If the extender used is water, it is also possible to use forexample organic solvents as auxiliary solvents. The following are mainlysuitable as liquid solvents: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, alcohols such as butanol or glycol andtheir ethers and esters, ketones such as acetone, methyl ethyl ketone,methyl isobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide or dimethyl sulphoxide, or else water. Liquefiedgaseous extenders or carriers are to be understood as meaning liquidswhich are gaseous at standard temperature and under atmosphericpressure, for example aerosol propellants such as halogenatedhydrocarbons, or else butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals such as highlydisperse silica, alumina and silicates. Suitable solid carriers forgranules are: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, or else syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks.Suitable emulsifiers and/or foam formers are: for example nonionic andanionic emulsifiers, such as polyoxyethylene fatty acid esters,polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycolethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or elseprotein hydrolysates. Suitable dispersants are: for examplelignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal pbthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or,in their formulations, also mixed with known fungicides, bactericides,acaricides, nematicides or insecticides in order thus, for example, towiden the spectrum of action or to prevent development of resistance. Inmany cases, synergistic effects are achieved here, i.e. the activity ofthe mixture exceeds the activity of the individual components

Examples of co-components in mixtures are the following compounds:

Fungicides:

aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,azaconazole, azoxystrobin,

benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,bromuconazole, bupirimate, buthiobate,

calcium polysulphide, capsimycin, captafol, captan, carbendazim,carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,

debacarb, dichloropben, diclobutrazole, diclofluanid, diclomezine,dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,ditalimfos, dithianon, dodemorph, dodine, drazoxolon,

edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,

famoxadon, fenapanil, fenarimol, fenbuconazole, fenfulram, fenitropan,fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide,fluquinconazole, flurprimidol, flusilazole, flusulfamide, flutolanil,flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,fuberidazole, fuiralaxyl, furametpyr, furcarbonil, furconazole,furconazole-cis, furmecyclox, guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),iprodione, irumamycin, isoprothiolane, isovaledione,

kasugamycin, kresoxim-methyl, copper preparations, such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulphate,copper oxide, oxine-copper and Bordeaux mixture,

mancopper, mancozeb, maneb, mefeirmzone, mepanipyrim, mepronil,metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,

nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,

ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin,

paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen,pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz,procymidone, propamocarb, propanosine-sodium, propiconazole, propineb,pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfiur,

quinconazole, quintozene (PCNB),

sulphur and sulphur preparations,

tebuconazole, teclofialam, tecnazene, tetcyclasis, tetraconazole,thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,triflumizole, triforine, triticonazole,

uniconazole,

validamycin A, vinclozolin, viniconazole,

zarilamide, zineb, ziram and also

Dagger G,

OK-8705,

OK-8801,

α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,

α-(2,4-dichlorophenyl)-β-methoxy-a-methyl-1H-1,2,4-triazole-1-ethanol,

α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,

(E)-a-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,

isopropyl{2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,

1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanoneO-(phenylmethyl) oxime,

1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,

1-(3,5-dichlorophenyl)3-(2-propenyl)2,5-pyrrolidinedione,

1-[(diiodomethyl)-sulphonyl]4methyl-benzene,

1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,

1-[[2-(4-chlorophenyl)3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,

1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,

1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,

2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4-trifluoro-methyl-1,3-thiazole-5-carboxanilide,

2,2-dichloro-N-[1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,

2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,

2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,

2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,

2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-a-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,

2-aminobutane,

2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,

2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,

2-phenylphenol (OPP),

3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,

3,5-dichloro-N-[cyano-[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,

3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,

3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,

4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,

8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,8-hydroxyquinoline sulphate,

9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,

bis-(1-methylethyl)3-methyl-4[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,

cis-1-(4-chlorophenyl)2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,

cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholinehydrochloride,

ethyl [(4-chlorophenyl)-azo]-cyanoacetate,

potassium hydrogen carbonate,

methanetetrathiol sodium salt,

methyl1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,

methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,

methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-turanyl)-acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

N-(4-cyclohexylphenyl)-1,4,5,6-tetrabydro-2-pyrimidinamine,

N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamnide,

N-(6-methoxy)-3-pyridinyl)-cyclopropanecarboxamide,

N-[2,2,2-trichloro-1-[(chloroacetyl)-ainino]-ethyl]-benzamide,

N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,

N-formyl-N-hydroxy-DL-alanine sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,

O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1,2,3-benzothiadiazole-7-carbothioate,

spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,

Bactericides:

bromopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

abarnectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin,amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M,azocyclotin,

Bacillus thuringiensis,4bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(tri-fluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC,brofenprox, bromophos A, bufencarb, buprofezin, butocarboxim,butylpyridaben,

cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethanimidamide,chlorpyrifos,

chlorpyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos,cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,cyromazine,

deltamethrin, demeton M, demeton S, demeton S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, etbofenprox,ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, fiubfenprox, furathiocarb, HCH, heptenophos,hexaflumuron, hexythiazox,

imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion,ivermectin, lambda-cyhalothrin, lufenuron,

malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde, methacrifos,methamidophos, methidathion, methiocarb, methomyl, metolcarb,milbemectin, monocrotophos, moxidectin,

naled, NC 184, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyretlumn,pyridaben, pyrimidifen, pyriproxifen,

quinalphos,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, zetamethrin.

It is also possible to admix other known active compounds, such asherbicides, fertilizers and growth-regulating substances.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. They are used in the customary manner, for example bypouring, spraying, atomizing, spreading, dusting, foaming, brushing onand the like. It is further possible to apply the active compounds bythe ultra-low volume method or to inject the active compoundformulation, or the active compound itself, into the soil. The seeds ofthe plants can also be treated.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the type of application. In the treatment of partsof plants, the active compound application rates are generally between0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. In thetreatment of seeds, the active compound application rates are generallybetween 0.001 and 50 g per kilogram of seed, preferably between 0.01 and10 g per kilogram of seed. In the treatment of the soil, the activecompound application rates are generally between 0.1 and 10,000 g/ha,preferably between 1 and 5000 g/ha.

The compositions used for protecting industrial materials generallycomprise the active compounds in an amount of from 1 to 95% by weight,preferably from 10 to 75% by weight.

The use concentrations of the active compounds according to theinvention depend on the species and the occurrence of the microorganismsto be controlled, and on the composition of the material to beprotected. The optimum amount to be used can be determined by testseries. In general, the use concentrations are in the range from 0.001to 5% by weight, preferably from 0.05 to 1.0% by weight, based on thematerial to be protected.

It is possible to increase the activity and the activity spectrum of theactive compounds to be used according to the invention in the protectionof materials, or of the compositions, concentrates or, quite generally,formulations preparable therefrom, by adding, if appropriate, otherantimicrobially active compounds, fungicides, bactericides, herbicides,insecticides or other active compounds to increase the activity spectrumor to obtain effects, such as, for example, additional protectionagainst insects. These mixtures may have a broader activity spectrumthan the compounds according to the invention.

The preparation and the use of active compounds according to theinvention are illustrated by the examples below.

PREPARATION EXAMPLES Example 1

At room temperature and with stirring, a solution of 110 mg (0.97 mmol)of 3-ethoxy-propyl isocyanate in 5 ml of absolute tetrabydrofuran isadded dropwise to a mixture of 350 mg (0.97 mmol) of3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)-2-[(4,5-dihydro-5-thiono-1,2,4-triazol-1-yl)-methyl]-oxirane,0.1 ml of triethylamine and 5 ml of absolute tetrahydrofliran. After theaddition has ended, the reaction mixture is heated at 60° C. for onehour and then concentrated under reduced pressure. The product thatremains is chromatographed over silica gel using a mixture ofcyclohexane/ethyl acetate =4:1. Concentration of the eluate gives 390 mg(82% of theory) of the substance of the formula shown above.

¹H-NMR spectrum (300 MHz, CDCl₃, TMS):

δ=10.0 (s, 1H); 8.4 (s, 1H); 7.6-7.3 (m, 6H); 7.0 (t, 2H, J=8.7 Hz); 5.1(d, 1H, J=14.9 Hz); 4.1 (s, 1H); 3.7 (d, 1H, J=14.9 Hz); 3.5-3.4 (m,6H); 1.9-1.8 (m, 2H); 1.2 (t, 3H, J=7.0 Hz) ppm.

The compounds listed in the table below are likewise prepared by themethod shown in Example 1:

TABLE 2 (I)

Example Melting No. R¹ R² R₃ point in ° C. 2

—CH₂—CH₂—O—CH₃ 105-107 3

—CH(CH₃)₂ 104-106 4

—C₁₂H₂₅-n 53-57 5

—CH(CH₃)₂ 100-101 6

—CH₂—CH₂—O—CH₃ 96-98

Example 7

¹H-NMR spectrum (400 MHz, CDCl₃, TMS):

δ=7.8 (s, 1H); 7.3-7.1 (m, 4H); 7.0-6.9 (m, 4H); 6.7 (s, 1H); 5.0 (d,1H); 4.7 (d, 1H); 4.5 (s, 1H); 3.7 (m, 1H); 1.0 (d, 6H, J=6.6 Hz) ppm.

Use Examples Example A

Erysiphe test (barley)/protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate.

After the spray coating has dried on, the plants are dusted with sporesof Erysiphe graminis f.sp. hordei

The plants are placed in a greenhouse at a temperature of approximately20° C. and a relative atmospheric humidity of approximately 80% topromote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infections are observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE A Erysiphe test (barley)/protective Active compound applicationrate Active compound g/ha Efficacy in % According to the invention: (1)125 100

(2) 125 100

(3) 125 100

(4) 125 100

Example B

Erysiphe test (barley)/curative

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are dusted with spores ofErysiphe graminis f.sp. hordei. 48Hours after the inoculation, theplants are sprayed with the preparation of active compound at the statedapplication rate.

The plants are placed in a greenhouse at a temperature of approximately20° C. and a relative atmospheric humidity of approximately 80% topromote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infections are observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE B Erysiphe test (barley)/curative Active compound application rateActive compound g/ha Efficacy in % According to the invention: (1) 250100

(4) 250 100

Example C

Erysiphe test (wheat)/protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate.

After the spray coating has dried on, the plants are dusted with sporesof Erysiphe graminis f.sp. tritici.

The plants are placed in a greenhouse at a temperature of approximately20° C. and a relative atmospheric humidity of approximately 80% topromote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infections are observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE C Erysiphe test (wheat)/protective Active compound applicationrate Active compound g/ha Efficacy in % According to the invention: (1)250 100

(3) 250 100

(4) 250 100

Example D

Leptosphaeria nodorum test (wheat)/protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are dusted with a sporesuspension of Leptosphaeria nodorum. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48Hours.

The plants are placed in a greenhouse at a temperature of approximately15° C. and a relative atmospheric humidity of 80%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infections are observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE D Leptosphaeria nodorum test (wheat)/protective Active compoundapplication rate Active compound g/ha Efficacy in % (1) 250 100

Example E

Puccinia test (wheat)/curative

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are sprayed with a Conidiasuspension of Puccinia recondita. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 Hours. Theplants are then sprayed with the preparation of active compound at thestated application rate.

The plants are placed in a greenhouse at a temperature of approximately20° C. and a relative atmospheric humidity of approximately 80%/o topromote the development of rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infections are observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE E Puccinia test (wheat)/curative Active compound application rateActive compound g/ha Efficacy in % According to the invention: (1) 125100

(2) 125 100

(3) 125 100

(4) 125 100

Example F

Puccinia test (wheat)/protective

Solvent: 25 parts by weight of N,N-dimethylacetamide

Emulsifier: 0.6 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are sprayed with a Conidiasuspension of Puccinia recondita. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 Hours.

The plants are placed in a greenhouse at a temperature of approximately20° C. and a relative atmospheric humidity of approximately 80% topromote the development of rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infections are observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE F Puccinia test (wheat)/protective Active compound applicationrate Active compound g/ha Efficacy in % According to the invention: (1)125 100

(2) 125 100

(4) 125 100

Example G

Podosphaera test (apple)/protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of the causative organism of apple mildew Podosphaeraleucotricha. The plants are then placed in a greenhouse at approximately23° C. and a relative atmospheric humidity of approximately 70%.

Evaluation was carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infections are observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE G Podosphaera test (apple)/protective Active compound applicationrate Active compound g/ha Efficacy in % Known from WO-A 96-38440: (A) 1092

1 57 According to the invention: (1) 10 100

1 65 (2) 10 100

1 88 (3) 10 100

1 80 (4) 10 100

Example H

Inhibition test on giant colonies of Basidiomycetes

Solvent: Dimethylsulphoxide

To produce a suitable preparation of active compound, 0.2 parts byweight of active compound are admixed to 99.8 parts by weight of theabovementioned solvent.

An agar, prepared by using malt extract peptone, is mixed in a liquidstate with the preparation of active compound at the particular desiredapplication rate. After solidification, the resultant nutrient medium isincubated at 26° C. with mycelium pieces punched out of colonies ofCoriolus versicolor.

Evaluation is carried out after 3 or 7 days' storage at 26° C. bymeasuring the growth of the mycelium and scoring the resultinginhibition in per cent in comparison to the untreated control. 0% meansan inhibition of growth which corresponds to that of the untreatedcontrol, while an inhibition of growth of 100% means that no growth ofmycelium is observed.

Active compounds, active compound concentrations and test results areshown in the table below.

TABLE H Inhibition test on giant colonies of Basidiomycetes Inhibitionin per cent of the radial growth of giant colonies at 6 ppm of activecompound according to Example Fungal species (1) (3) (5) Coriolusversicolor 100 100 100

What is claimed is:
 1. An oxiranyl-triazolinethione of the formula

in which R¹ represents alkyl having 1 to 4 carbon atoms, halogenoalkylhaving 1 to 4 carbon atoms and 1 to 5Halogen atoms, optionallyhalogen-substituted cycloalkyl having 3 to 7 carbon atoms, naphthyl orphenyl which is optionally mono- to trisubstituted by identical ordifferent substituents from the group consisting of halogen, nitro,phenyl, phenoxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to5Halogen atoms, R² represents phenyl which is optionally mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5halogen atoms and halogenoalkylthio having 1 to 4 carbon atoms and 1 to5Halogen atoms and R³ represents alkoxyalkyl, isopropyl or n-dodecyl. 2.An oxiranyl-triazolinethione of the formula (I) according to claim 1 inwhich R¹ represents methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, iso-butyl, tert-butyl, fluoro-tert-butyl,difluoro-tert-butyl, cycloalkyl having three to six carbon atoms whichis optionally mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine andbromine, represents naphthyl or represents phenyl which may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, nitro, phenyl, phenoxy,methyl, ethyl, tert-butyl, methoxy, ethoxy, trifluoromethyl,trichloromethyl, difluoromethyl, difluoro-chloromethyl,trifluoromethoxy, difluoromethoxy and trifluoromethylthio, R² representsphenyl which may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, trifluoromethyl,trichloromethyl, difluoromethyl, difluorochloromethyl, trifluoromethoxy,difluoromethoxy and trifluoromethylthio, and R³ represents alkoxyalkylhaving 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atomsin the alkyl moiety and also represents isopropyl or n-dodecyl.
 3. Amicrobicidal composition comprising a microbicidally effective amount ofan oxiranyl-triazolinethione of the formula (I) according to claim 1, anextender and/or a surfactant.
 4. A method for controlling undesirablemicroorganisms in crop protection and in the protection of materialscomprising applying a microbidically effective amount of anoxiranyl-triazolinethione of the formula (I) according to claim
 1. 5.Oxiranyl-triazolinethione according to claim 1, characterized by theformula


6. Oxiranyl-triazolinethione according to claim 1, characterized by theformula


7. An It Oxiranyl-triazolinethione according to claim 1, characterizedby the formula


8. An oxiranyl-triazolinethione according to formula (I) of claim 1,wherein R¹ represents phenyl which may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, nitro, phenyl, phenoxy, methyl, ethyl,tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl,difluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxyand trifluoromethylthio.
 9. An oxiranyl-triazolinethione according toformula (I) of claim 1, wherein R² represents phenyl which may be mono-to trisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, isopropyl,tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl,difluoromethyl, difluorochloromethyl, trifluoromethoxy, difluoromethoxyand trifluoromethylthio.
 10. An oxiranyl-triazolinethione according toformula (I) of claim 1, wherein R³ represents alkoxyalkyl having 1 to 4carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkylmoiety and also represents isopropyl or n-dodecyl.